Compositions and processes for the oxidation dyeing of keratin fibers with oxidation bases, a meta-aminophenol, and y-hyroxyindoline

ABSTRACT

A composition for the oxidation dyeing of keratin fibers, in particular human keratin fibers such as the hair, comprising at least one suitably selected oxidation base, at least one meta-aminophenol as first coupler and 4-hydroxyindoline and/or at least one of the addition salts thereof with an acid as second coupler, and dyeing processes using this composition with an oxidizing agent.

The present invention relates to a composition for the oxidation dyeingof keratin fibres, in particular human keratin fibres such as the hair,comprising at least one suitably selected oxidation base, at least onemeta-aminophenol as first coupler and 4-hydroxyindoline and/or at leastone of the addition salts thereof with an acid as second coupler, aswell as to the dyeing process using this composition with an oxidizingagent.

It is known to dye keratin fibres, and in particular human hair, withdye compositions containing oxidation dye precursors, in particularortho- or para-phenylenediamines, ortho- or para-aminophenols, which aregenerally referred to as oxidation bases. The oxidation dye precursors,or oxidation bases, are colourless or weakly coloured compounds which,when combined with oxidizing products, may give rise to colouredcompounds and dyes by a process of oxidative condensation.

It is also known that the shades obtained with these oxidation bases maybe varied by combining them with couplers or coloration modifiers, thelatter being chosen in particular from aromatic meta-diamines,meta-aminophenols, meta-diphenols and certain indole or indolinecompounds.

The variety of molecules used as oxidation bases and couplers makes itpossible to obtain a wide range of colours.

The so-called "permanent" coloration obtained by means of theseoxidation dyes must moreover satisfy a certain number of requirements.Thus, it must have no toxicological drawbacks and it must allow shadesof the desired intensity to be obtained and have good resistance toexternal agents (light, bad weather, washing, permanent-waving,perspiration and rubbing).

The dyes must also allow white hairs to be covered and, lastly, theymust be as unselective as possible, that is to say that they must allowthe smallest possible differences in coloration to be produced over theentire length of the same keratin fibre, which may indeed be differentlysensitized (i.e. damaged) between its tip and its root.

In order to produce natural or highlighted shades, it is common to usedye compositions comprising a para-phenylenediamine derivative asoxidation base and a meta-aminophenol derivative as coupler. However,the coloration obtained with such dye compositions are not entirelysatisfactory since they generally have mediocre light-fastness.

Moreover, compositions for the oxidation dyeing of keratin fibres inalkaline medium, comprising at least one oxidation base such as, forexample, para-phenylenediamine or a para-phenylenediamine derivative, incombination with an indoline coupler such as, for example,4-hydroxyindoline, have already been proposed, in particular in patentapplication FR 2,008,797. These compositions are not entirelysatisfactory either since they lead to colorations which also havemediocre light-fastness.

Now, the Applicant has just discovered that it is possible to obtainnovel dyes in acidic, neutral or alkaline medium, which are capable ofgenerating intense colorations that offer good resistance to the variousattacking factors to which the hair may be subjected and in particularto the action of light, by combining at least one suitably selectedoxidation base, at least one meta-aminophenol as first coupler and4-hydroxyindoline and/or at least one of the addition salts thereof withan acid as second coupler. This result is all the more unexpected andsurprising since, as indicated above, when the two couplers are usedseparately in combination with the same oxidation base in accordancewith the invention, they lead to colorations with poor light-fastness onhair.

This discovery forms the basis of the present invention.

A first subject of the invention is thus a composition for the oxidationdyeing of keratin fibres, and in particular human keratin fibres such asthe hair, characterized in that it comprises, in a medium which issuitable for dyeing:

at least one oxidation base chosen from para-phenylenediamines and/orbis(phenyl)alkylenediamines,

at least one meta-aminophenol as first coupler,

at least one second coupler chosen from 4-hydroxyindoline and theaddition salts thereof with an acid.

The oxidation dyeing composition in accordance with the invention makesit possible to obtain intense colorations in a variety of shades, thesecolorations being relatively unselective and having excellent fastnessproperties both to atmospheric agents such as the light and bad weatherand to perspiration and the various treatments to which the hair may besubjected (shampooing, permanent waving). These properties areparticularly noteworthy with regard to light.

A subject of the invention is also a process for the oxidation dyeing ofkeratin fibres using this composition.

Among the meta-aminophenols which can be used as first coupler in thecompositions in accordance with the invention, mention may be made ofthe compounds corresponding to formula (I) below, and the addition saltsthereof with an acid: ##STR1## in which: R₁ and R₄, which may beidentical or different, represent a hydrogen or halogen atom or a C₁ -C₄alkyl or C₁ -C₄ alkoxy radical,

R₂ represents a hydrogen atom or a C₁ -C₄ alkyl, C₁ -C₄monohydroxyalkyl, C₂ -C₄ polyhydroxyalkyl, C₁ -C₄ trifluoroalkyl orcarbamoylmethyl radical,

R₃ represents a hydrogen atom or a C₁ -C₄ alkyl radical or alternativelyforms, with R₂ and the nitrogen atom, a 5- or 6-membered heterocycle,

R₅ represents a hydrogen or halogen atom or a C₁ -C₄ alkyl, C₁ -C₄alkoxy, C₁ -C₄ monohydroxyalkyl or C₂ -C₄ polyhydroxyalkyl radical.

Among the meta-aminophenols of formula (I) above which are used as firstcoupler in the dye compositions in accordance with the invention,mention may be made more particularly of 3-aminophenol,5-amino-2-methoxyphenol, 5-amino-4-chloro-2-methylphenol,5-amino-2,4-dimethoxyphenol, 5-amino-2-β-hydroxyethyloxyphenol,5-N-(β-hydroxyethyl)amino-4-methoxy-2-methylphenol,5-amino-4-methoxy-2-methylphenol,5-N-(β-hydroxypropyl)amino-2-methylphenol,5-N-(γ-hydroxyethyl)amino-2-methylphenol, 5-amino-2-methylphenol,3-N-(carbamoylmethyl)aminophenol,5-N-(carbamoylmethyl)amino-2-methylphenol, 3-N,N-(dimethyl)aminophenol,3-N,N-(diethyl)aminophenol, 3-amino-2,4-dichlorophenol,3-amino-4,6-dichlorophenol, 5-amino-6-chloro-2-methylphenol,2-chloro-5-N-(2',2',2'-trifluoroethyl)aminophenol,5-amino-4-chloro-2-methylphenol and 3-N-(cyclopentyl)aminophenol, andthe addition salts thereof with an acid.

Among the para-phenylenediamines which can be used as oxidation base inthe compositions in accordance with the invention, mention may be madeof the compounds corresponding to formula (II) below, and the additionsalts thereof with an acid: ##STR2## in which: R₆, R₇ and R₈, which maybe identical or different, represent a hydrogen or halogen atom or a C₁-C₄ alkyl, C₁ -C₄ alkoxy, sulpho, carboxyl, C₁ -C₄ monohydroxyalkyl orC₂ -C₄ polyhydroxyalkyl radical,

R₉ and R₁₀, which may be identical or different, represent a hydrogenatom, a C₁ -C₄ alkyl, C₁ -C₄ monohydroxyalkyl, C₂ -C₄ polyhydroxyalkyl,C₁ -C₄ alkoxy(C₁ -C₄) alkyl, carbamyl(C₁ -C₄) alkyl, C₁ -C₄mesylaminoalkyl, acetylamino(C₁ -C₄) alkyl, C₁ -C₄ ureidoalkyl, carb(C₁-C₄) alkoxyamino(C₁ -C₄)alkyl, C₁ -C₄ sulphoalkyl, piperidino (C₁ -C₄)alkyl, morpholino (C₁ -C₄)alkyl or phenyl radical or a phenyl radicalsubstituted in the para position with an amino group, or alternativelyR₉ and R₁₀ form, together with the nitrogen atom to which they areattached, a piperidino or morpholino heterocycle;

it being understood that if R₉ and R₁₀ do not simultaneously represent ahydrogen atom, then at least one of the radicals R₆ and R₈ mustrepresent a hydrogen atom.

Among the C₁ -C₄ alkyl and C₁ -C₄ alkoxy radicals of formulae (I) and(II) above, mention may be made in particular of the methyl, ethyl,propyl, methyloxy and ethyloxy radicals.

Among the para-phenylenediamines of formula (II) above which are used asoxidation base in the dye compositions in accordance with the invention,mention may be made more particularly of para-phenylenediamine,para-toluylene-diamine, 2-chloro-para-phenylenediamine,2,3-dimethyl-para-phenylenediamine, 2,6-dimethyl-para-phenylene-diamine,2,6-diethyl-para-phenylenediamine, 2,5-dimethyl-para-phenylenediamine,2-methyl-5-methoxy-para-phenylenediamine,2,6-dimethyl-5-methoxy-para-phenylenediamine,N,N-dimethyl-para-phenylenediamine, N,N-diethyl-para-phenylenediamine,N,N-dipropyl-para-phenylenediamine, 4-amino-N,N-diethyl-3-methylaniline,N,N-bis(β-hydroxyethyl)-para-phenylenediamine,4-amino-N,N-bis(β-hydroxyethyl)-3-methylaniline,4-amino-3-chloro-N,N-bis(β-hydroxyethyl)aniline, 4-amino-N,N-(ethyl,carbamylmethyl)aniline, 4-amino-3-methyl-N,N-(ethyl,carbamylmethyl)aniline, 4-amino-N,N-(ethyl, β-piperidinoethyl)aniline,4-amino-3-methyl-N,N-(ethyl, β-piperidinoethyl)aniline,4-amino-N,N-(ethyl, β-morpholinoethyl)aniline,4-amino-3-methyl-N,N-(ethyl, β-morpholinoethyl)aniline,4-amino-N,N-(ethyl, β-acetylaminoethyl)aniline,4-amino-N-(β-methoxyethyl)aniline, 4-amino-3-methyl-N,N-(ethyl,β-acetylaminoethyl)aniline, 4-amino-N,N-(ethyl,β-mesylaminoethyl)aniline, 4-amino-3-methyl-N,N-(ethyl,β-mesylaminoethyl)aniline, 4-amino-N,N-(ethyl, β-sulphoethyl)aniline,4-amino-3-methyl-N,N-(ethyl, β-sulphoethyl)-aniline,N-[(4'-amino)phenyl]morpholine, N-[(4'-amino)phenyl]piperidine,2-β-hydroxyethyl-para-phenylenediamine, 2-fluoro-para-phenylenediamine,2-carboxy-para-phenylenediamine, 2-sulpho-para-phenylenediamine,2-isopropyl-para-phenylenediamine,N-(β-hydroxypropyl)-para-phenylenediamine,2-hydroxymethyl-para-phenylene-diamine,N,N-dimethyl-3-methyl-para-phenylenediamine, N,N-(ethyl,β-hydroxyethyl)-para-phenylenediamine, N-(β,γ-dihydroxypropyl)-para-phenylenediamine,N-(4'-aminophenyl)-para-phenylenediamine, N-phenyl-para-phenylenediamineand 2-β-hydroxyethyloxy-para-phenylenediamine, and the addition saltsthereof with an acid.

Among the para-phenylenediamines of formula (II) above which are used asoxidation base in the dye compositions in accordance with the invention,para-phenylenediamine, para-toluylenediamine,2,6-dimethyl-para-phenylenediamine,2-β-hydroxyethyl-para-phenylene-diamine,2-isopropyl-para-phenylenediamine,N-(β-hydroxypropyl)-para-phenylenediamine,N,N-bis-(β-hydroxyethyl)-para-phenylenediamine and4-amino-N-(β-methoxyethyl)aniline, and the addition salts thereof withan acid, are more particularly preferred.

Among the bis(phenyl)alkylenediamines which can be used as oxidationbase in the dye compositions in accordance with the invention, mentionmay be made more particularly of the compounds corresponding to formula(III) below, and the addition salts thereof with an acid: ##STR3## inwhich: Z₁ and Z₂, which may be identical or different, represent ahydroxy radical or a radical NHR₁₄ in which R₁₄ represents a hydrogenatom or a C₁ -C₄ alkyl radical,

R₁₁ represents a hydrogen atom or a C₁ -C₄ alkyl, C₁ -C₄monohydroxyalkyl or C₂ -C₄ polyhydroxyalkyl radical or a C₁ -C₄aminoalkyl radical in which the amino residue may be substituted,

R₁₂ and R₁₃, which may be identical or different, represent a hydrogenor halogen atom or a C₁ -C₄ alkyl radical,

Y represents a radical taken from the group consisting of the followingradicals: --(CH₂)_(n) --; --(CH₂)_(m) --O--(CH₂)_(m) --; --(CH₂)_(m)CHOH--(CH₂)_(m) -- and ##STR4## in which n is an integer between 0 and 8inclusive and m is an integer between 0 and 4 inclusive.

Among the C₁ -C₄ alkyl radicals of formula (III) above, mention may bemade in particular of the methyl, ethyl and propyl radicals.

Among the bis(phenyl)alkylenediamines of formula (III) above which areused as oxidation base in the dye compositions in accordance with theinvention, mention may be made more particularly ofN,N'-bis(β-hydroxyethyl)-N,N'-bis(4'-aminophenyl)-1,3-diaminopropanol,N,N'-bis(β-hydroxyethyl)-N,N'-bis(4'-aminophenyl)ethylenediamine,N,N'-bis-(4-aminophenyl)tetramethylenediamine,N,N'-bis-(β-hydroxyethyl)-N,N'-bis(4-aminophenyl)tetramethylenediamine,N,N'-bis(4-methylaminophenyl)tetramethylenediamine andN,N'-bis(ethyl)-N,N'-bis(4'-amino-3'-methylphenyl)ethylenediamine, andthe addition salts thereof with an acid.

Among these bis(phenyl)alkylenediamines of formula (III),N,N'-bis(β-hydroxyethyl)-N,N'-bis(4'-aminophenyl)-1,3-diaminopropanol isparticularly preferred.

The addition salts with an acid which can be used in the context of thedye compositions of the invention are chosen in particular from thehydrochlorides, hydrobromides, sulphates and tartrates.

The oxidation base(s) in accordance with the invention, that is to saythe para-phenylenediamine(s) and/or the bis(phenyl)alkylenediamine(s),preferably represent from 0.0005 to 12% by weight approximately relativeto the total weight of the dye composition, and even more preferablyfrom 0.005 to 6% by weight approximately relative to this weight.

The meta-aminophenol(s) of formula (I) which are used as first couplerin the dye compositions in accordance with the invention preferablyrepresent from 0.0001 to 10% by weight approximately relative to thetotal weight of the dye composition and even more preferably from 0.005to 5% by weight approximately relative to this weight.

The 4-hydroxyindoline and/or the addition salt(s) thereof with an acidwhich are used as second coupler in the dye compositions in accordancewith the invention preferably represent from 0.0001 to 10% by weightapproximately relative to the total weight of the dye composition andeven more preferably from 0.005 to 5% by weight approximately relativeto this weight.

The medium which is suitable for dyeing (or the support) generallyconsists of water or of a mixture of water and at least one organicsolvent to solubilize the compounds which would not be sufficientlysoluble in water. Organic solvents which may be mentioned, for example,are C₁ -C₄ lower alkanols such as ethanol and isopropanol; glycerol;glycols and glycol ethers such as 2-butoxyethanol, propylene glycol,propylene glycol monomethyl ether, diethylene glycol monoethyl ether andmonomethyl ether, and aromatic alcohols such as benzyl alcohol orphenoxyethanol, similar products and mixtures thereof.

The solvents may be present in proportions preferably of between 1 and40% by weight approximately relative to the total weight of the dyecomposition, and even more preferably of between 5 and 30% by weightapproximately.

The pH of the dye composition in accordance with the invention isgenerally between 3 and 12. It may be adjusted to the desired valueusing acidifying or basifying agents usually used in the dyeing ofkeratin fibres.

Among the acidifying agents which may be mentioned, by way of example,are inorganic or organic acids such as hydrochloric acid,orthophosphoric acid, carboxylic acids such as tartaric acid, citricacid and lactic acid, and sulphonic acids.

Among the basifying agents which may be mentioned, by way of example,are aqueous ammonia, alkaline carbonates, alkanolamines such as mono-,di- and triethanolamines and derivatives thereof, sodium hydroxide orpotassium hydroxide and the compounds of formula (IV) below: ##STR5## inwhich R is a propylene residue optionally substituted with a hydroxylgroup or a C₁ -C₄ alkyl radical; R₁₅, R₁₆, R₁₇ and R₁₈, which may beidentical or different, represent a hydrogen atom or a C₁ -C₄ alkyl orC₁ -C₄ hydroxyalkyl radical.

In addition to the dyes defined above, the dye composition in accordancewith the invention can also contain other oxidation bases and/or othercouplers and/or direct dyes, in particular in order to modify the shadesor to enrich them with highlights.

The dye composition according to the invention may also include variousadjuvants used conventionally in compositions for dyeing the hair, suchas anionic, cationic, nonionic, amphoteric or zwitterionic surfactantsor mixtures thereof, anionic, cationic, nonionic, amphoteric orzwitterionic polymers or mixtures thereof, inorganic or organicthickeners, antioxidants, penetration agents, sequestering agents,fragrances, buffers, dispersing agents, conditioners such as, forexample, silicones, film-forming agents, preserving agents andopacifying agents.

Obviously, a person skilled in the art will take care to select theoptional complementary compound(s) mentioned above such that theadvantageous properties intrinsically associated with the ternarycombination in accordance with the invention are not, or are notsubstantially, adversely affected by the addition or additionsenvisaged.

The dye composition according to the invention may be in various forms,such as in the form of liquids, creams, gels or any other form which issuitable for dyeing keratin fibres, and in particular human hair.

A subject of the invention is also a process for dyeing keratin fibres,and in particular human keratin fibres such as the hair, using the dyecomposition as defined above.

According to this process, at least one dye composition as defined aboveis applied to the fibres, the colour being developed at acidic, neutralor alkaline pH using an oxidizing agent which is added to the dyecomposition only at the time of use, or which is present in an oxidizingcomposition that is applied simultaneously or sequentially in a separatemanner. According to a particularly preferred embodiment of the dyeingprocess according to the invention, the dye composition described aboveis mixed, at the time of use, with an oxidizing composition containing,in a medium which is suitable for dyeing, at least one oxidizing agentpresent in an amount which is sufficient to develop a coloration. Themixture obtained is then applied to the keratin fibres and is left inplace for 3 to 50 minutes approximately, preferably 5 to 30 minutesapproximately, after which the fibres are rinsed, washed with shampoo,rinsed again and dried.

The oxidizing agent present in the oxidizing composition as definedabove may be chosen from the oxidizing agents conventionally used forthe oxidation dyeing of keratin fibres, and among which mention may bemade of hydrogen peroxide, urea peroxide, alkali metal bromates andpersalts such as perborates and persulphates. Hydrogen peroxide isparticularly preferred.

The pH of the oxidizing composition containing the oxidizing agent asdefined above is such that, after mixing with the dye composition, thepH of the resulting composition applied to the keratin fibres preferablyvaries approximately between 3 and 12 and even more preferably between 5and 11. It is adjusted to the desired value using acidifying orbasifying agents usually used in the dyeing of keratin fibres and as aredefined above.

The oxidizing composition as defined above may also include variousadjuvants used conventionally in compositions for dyeing the hair and asare defined above.

The composition which is finally applied to the keratin fibres may be invarious forms, such as in the form of liquids, creams, gels or any otherform which is suitable for dyeing keratin fibres, and in particularhuman hair.

Another subject of the invention is a multi-compartment device or dyeing"kit" or any other multi-compartment packaging system a firstcompartment of which contains the dye composition as defined above and asecond compartment of which contains the oxidizing composition asdefined above. These devices may be equipped with a means which makes itpossible to deliver the desired mixture onto the hair, such as thedevices described in patent FR-2,586,913 in the name of the Applicant.

The examples which follow are intended to illustrate the inventionwithout, however, limiting the scope thereof.

EXAMPLES

Dye compositions 1 to 3 below were prepared:

    ______________________________________                                         COMPOSITION              2(*)( )  3(**)                                      ______________________________________                                        Para-phenylenediamine (in                                                                          3 × 10.sup.-3                                                                 3 × 10.sup.-3                                                                   3 × 10.sup.-3                        moles)                                                                        3-Aminophenol (in moles)                                                                             3 × 10.sup.-3                                                                 --       1.5 × 10.sup.-3                   4-Hydroxyindoline (in moles)                                                                       --       3 × 10.sup.-3                                                                1.5 × 10.sup.-3                      Common dye support                                                                                        (***)*)                                                                                      (***)                              Demineralized water qs                                                                                 100 g                                                                            100 g   100 g                                     ______________________________________                                          (*): dye composition not forming part of the invention                       (**): dye compositon in accordance with the invention                         (***): common dye support:                                               

    Oleyl alcohol polyglycerolated with                                                                   4.0    g                                              2 mol of glycerol                                                             Oleyl alcohol polyglycerolated with                                                                     5.69 g A.M.                                         4 mol of glycerol, containing 78%                                             active material (A.M.)                                                        Oleic acid                     g                   3.0                        Oleylamine containing 2 mol of                                                                               7.0                                                                           g                                              ethylene oxide, sold under the trade                                          name Ethomeen 012 by the company Akzo                                         Diethylaminopropyl laurylamino-                                                                             3.0                                                                            g A.M.                                         succinamate, sodium salt,                                                     containing 55% A.M.                                                           Oleyl alcohol                  g                5.0                           Oleic acid diethanolamide                                                                                    g   12.0                                       Propylene glyco                g              3.5                             Ethyl alcohol                  g                7.0                           Dipropylene glycol             g           0.5                                Propylene glycol monomethyl ether                                                                         9.0                                                                              g                                              Sodium metabisulfite as an aqueous                                                                       0.455                                                                             g A.M.                                         solution containing 35% A.M.                                                  Ammonium acetate               g             0.8                              Antioxidant, sequestering agent                                                                             q.s.                                            Fragrance, preserving agent                                                                                     q.s.                                        Aqueous axnmonia containing 20% NH.sub.3                                                               10.0  g                                              ______________________________________                                    

At the time of use, each dye composition 1 to 3 was mixed with an equalweight amount of 20-volumes aqueous hydrogen peroxide solution (6% byweight).

Each resulting mixture was applied for 30 minutes to locks of naturalgrey hair containing 90% white hairs. The locks of hair were thenrinsed, washed with a standard shampoo and then dried.

The colour of the locks was then evaluated in the Munsell system using aMinolta CM 2002 calorimeter.

The locks of hair thus dyed then underwent a light-fastness test. Themachine used to carry out the light-fastness test was a Hanau Suntestmachine equipped with a xenon lamp allowing the passage of UV rays overa wavelength range of between 300 and 830 nm.

The locks were attached to a cardboard support which was introduced intothe machine and irradiated for 18 hours, which corresponds to aboutthree weeks of exposure to natural light.

The xenon lamp was cooled, during the test, using an air flow of about60 m³ /hour. A second air flow of about 60 m³ /hour also cooled thelocks.

The temperature of the locks was about 45° C.

The light intensity falling on the locks was about 150 klx.

The intensity of the irradiation was about 830 W/m².

The colour of the locks after the test was again measured in the Munsellsystem using a Minolta CM 2002 colorimeter.

The difference in colour of each lock before and after thelight-fastness test reflects the degradation in coloration due to theaction of light, and was calculated by applying the Nickerson formula:ΔE=0.4 CoΔH+6ΔV+3ΔC, as described, for example, in "Couleur, Industrieet Technique"; pages 14-17; vol. No. 5; 1978.

In this formula, ΔE represents the difference in colour between twolocks, ΔH, ΔV and ΔC represent the variation in absolute value of theparameters H, V and C, and Co represents the purity of the lock againstwhich it is desired to evaluate the difference in colour (purity of thelock before the test).

The results are given in Table II below:

    ______________________________________                                        Compo- Colour                Degradation of the                               sition before the Colour after                                                                             colour                                           Example                                                                              test       the test   ΔH                                                                           ΔV                                                                           ΔC                                                                           ΔE                          ______________________________________                                        1(1)   10RP2.4/1.4                                                                              5.2R2.7/1.2                                                                              5.2  0.3  0.2  5.3                               2(2)   4.2YR2.7/1.4                                                                             5.6YR3.3/1.5                                                                             1.4  0.6  0.1  4.7                               3(3)   6.9R2.7/1.4                                                                              0.4YR2.8/1.3                                                                             3.5  0.1  0.1  2.9                               ______________________________________                                    

These results show clearly that the dye composition of Example 3 inaccordance with the invention, that is to say the composition comprisingan oxidation base (para-phenylenediamine), in combination withmeta-aminophenol as first coupler and 4-hydroxyindoline as secondcoupler, leads to a coloration which has markedly better light-fastnessthan the colorations obtained with the comparative dye compositions ofExamples 1 and 2 (which do not form part of the invention since theycontain only one of the two couplers).

I claim:
 1. A composition for the oxidation dyeing of keratin fiberscomprising, in a medium suitable for dyeing:at least one oxidation basewhich is a para-phenylenediamine, a bis(phenyl) alkylenediamine or anacid addition salt thereof, at least one first coupler which is ameta-aminophenol or an acid addition salt thereof, and at least onesecond coupler which is 4-hydroxyindoline or an acid addition saltthereof, wherein said at least one oxidation base and said at least onefirst and second couplers are present in amounts effective tooxidatively dye said keratin fibers.
 2. A composition according to claim1, wherein said keratin fibers are human hair.
 3. A compositionaccording to claim 1, wherein said meta-aminophenols are selected fromcompounds corresponding to formula (1): ##STR6## in which: R₁ and R₄each independently represent a hydrogen or halogen atom or a C₁ -C₄alkyl or C₁ -C₄ alkoxy radical,R₂ represents a hydrogen atom or a C₁ -C₄alkyl, C₁ -C₄ monohydroxyalkyl, C₂ -C₄ polyhydroxyalkyl, C₁ -C₄trifluoroalkyl or carbamoylmethyl radical, R₃ represents a hydrogen atomor a C₁ -C₄ alkyl radical or alternatively R₂ and R₃ form, together withthe nitrogen atom to which they are attached, a 5- or 6-memberedheterocycle, and R₅ represents a hydrogen or halogen atom or a C₁ -C₄alkyl, C₁ -C₄ monohydroxyalkyl or C₂ -C₄ polyhydroxyalkyl radical.
 4. Acomposition according to claim 3, wherein said meta-aminophenol isselected from 3-aminophenol, 5-amino-2-methoxyphenol,5-amino4-chloro-2-methyl-phenol, 5-amino-2,4-dimethoxyphenol,5-amino-2-β-hydroxyethyloxyphenol,5-N-(β-hydroxyethyl)amino-4-methoxy-2-methylphenol,5-amino-4-methoxy-2-methylphenol,5-N-(γ-hydroxypropyl)amino-2-methylphenol,5-N-(β-hydroxyethyl)amino-2-methyl-phenol, 5-amino-2-methylphenol,3-N-(carbamoylmethyl)-aminophenol,5-N-(carbamoylmethyl)amino-2-methylphenol, 3-N, N-(dimethyl)aminophenol,3-N,N-(diethyl)aminophenol, 3-amino-2,4-dichlorophenol,3-amino-4,6-dichlorophenol, 5-amino-6-chloro-2-methylphenol,2-chloro-5-N-(2',2',2'-trifluoroethyl)aminophenol,5-amino-4-chloro-2-methylphenol or 3-N-(cyclopentyl)-aminophenol.
 5. Acomposition according to claim 1, wherein said para-phenylenediaminesare selected from compounds of formula (II): ##STR7## in which: R₆, R₇and R₈ each independently represent a hydrogen or halogen atom or a C₁-C₄ alkyl, C₁ -C₄ alkoxy, sulpho, carboxyl, C₁ -C₄ monohydroxyalkyl orC₂ -C₄ polyhydroxyalkyl radical,R₉ and R₁₀ each independently representa hydrogen atom, a C₁ -C₄ alkyl, C₁ -C₄ monohydroxyalkyl, C₂ -C₄polyhydroxyalkyl, C₁ -C₄ alkoxy(C₁ -C₄)alkyl, carbamyl(C₁ -C₄)alkyl, C₁-C₄ mesylaminoalkyl, acetylamino(C₁ -C₄)alkyl, C₁ -C₄ ureidoalkyl,carb(C₁ -C₄)alkoxyamino(C₁ -C₄)alkyl, Cl-C₄ sulphoalkyl, piperidino(C₁-C₄)alkyl, morpholino(C₁ -C₄)alkyl or phenyl radical or a phenyl radicalsubstituted in the para position with an amino group, or alternativelyR₉ and R₁₀ form, together with the nitrogen atom to which they areattached, a piperidino or morpholino heterocycle; wherein if R₉ and R₁₀do not simultaneously represent a hydrogen atom, then at least one ofthe radicals R₈ and R₆ must represent a hydrogen atom.
 6. A compositionaccording to claim 5, wherein said para-phenylenediamines are selectedfrom para-phenylenediamine, para-toluylenediamine,2-chloro-para-phenylenediamine, 2,3-dimethyl-para-phenylenediamine,2,6-dimethyl-para-phenylenediamine, 2,6-diethyl-para-phenylenediamine,2,5-dimethyl-para-phenylenediamine,2-methyl-5-methoxy-para-phenylenediamine,2,6-dimethyl-5-methoxy-para-phenylenediamine,N,N-dimethyl-para-phenylenediamine, N,N-diethyl-para-phenylenediamine,N,N-dipropyl-para-phenylenediamine, 4-amino-N,N-diethyl-3-methylaniline,N,N-bis(β-hydroxyethyl)-para-phenylenediamine,4-amino-N,N-bis(β-hydroxyethyl)-3-methylaniline,4-amino-3-chloro-N,N-bis(β-hydroxyethyl)aniline, 4-amino-N,N-(ethyl,carbamylmethyl)aniline, 4-amino-3-methyl-N,N-(ethyl,carbamylmethyl)aniline, 4-amino-N,N-(ethyl, β-piperidinoethyl)aniline,4-amino-3-methyl-N,N-(ethyl, β-piperidinoethyl)aniline,4-amino-N,N-(ethyl, β-morpholinoethyl)aniline,4-amino-3-methyl-N,N-(ethyl, β-morpholinoethyl)aniline,4-amino-N,N-(ethyl, β-acetylaminoethyl)aniline,4-amino-N-(β-methoxyethyl)-aniline, 4-amino-3-methyl-N,N-(ethyl,β-acetylamino-ethyl)aniline, 4-amino-N,N-(ethyl,β-mesylaminoethyl)-aniline, 4-amino-3-methyl-N,N-(ethyl,β-mesylamino-ethyl)aniline, 4-amino-N,N-(ethyl, β-sulphoethyl)-aniline,4-amino-3-methyl-N,N-(ethyl, β-sulphoethyl)-aniline,N-[(4'-amino)phenyl]morpholine, N-[(4'-amino)-phenyl]piperidine,2-β-hydroxyethyl-para-phenylene-diamine, 2-fluoro-para-phenylenediamine,2-carboxy-para-phenylenediamine, 2-sulpho-para-phenylenediamine,2-isopropyl-para-phenylenediamine,N-(β-hydroxypropyl)-para-phenylenediamine,2-hydroxymethyl-para-phenylene-diamine,N,N-dimethyl-β-methyl-para-phenylenediamine, N,N-(ethyl,β-hydroxyethyl)-para-phenylenediamine, N-(β,γ-dihydroxypropyl)-para-phenylenediamine,N-(4'-aminophenyl)-para-phenylenediamine, N-phenyl-para-phenylenediamineor 2-β-hydroxyethyloxy-para-phenylenediamine.
 7. A composition accordingto claim 6, wherein said para-phenylenediamine is selected frompara-phenylenediamine, para-toluylenediamine,2,6-dimethyl-para-phenylenediamine,2-β-hydroxyethyl-para-phenylenediamine,2-isopropyl-para-phenylenediamine,N-(β-hydroxypropyl)-para-phenylenediamine,N,N-bis-(β-hydroxyethyl)-para-phenylenediamine or4-amino-N-(β-methoxyethyl)aniline.
 8. A composition according to claim1, wherein said bis(phenyl)alkylenediamines are selected from compoundsof formula (Ill): ##STR8## in which: Z₁ and Z₂ each independentlyrepresent a hydroxyl radical or a radical NHR₁₄ in which R₁₄ representsa hydrogen atom or a C₁ -C₄ alkyl radical,R₁₁ represents a hydrogen atomor a C₁ -C₄ alkyl, C₁ -C₁₄ monohydroxyalkyl or C₂ -C₆ polyhydroxyalkylradical or a C₁ -C₄ aminoalkyl radical in which the amino residue may besubstituted, R₁₂ and R₁₃ each independently represent a hydrogen orhalogen atom or a C₁ -C₄ alkyl radical, Y represents one of thefollowing radicals: ##STR9## in which: n is an integer ranging from 0 to8, and m is an integer ranging from 0 to
 4. 9. A composition accordingto claim 8, wherein said bis(phenyl)alkylenediamine is selected fromN,N'-bis(β-hydroxy-ethyl)-N,N'-bis(4'-aminophenyl)-1,3-diaminopropanol,N,N'-bis(β-hydroxyethyl)-N,N'-bis(4'-aminophenyl)-ethylenediamine,N,N'-bis(4-aminophenyl)tetramethylenediamine,N,N'-bis-(β-hydroxyethyl)-N,N'-bis-(4-aminophenyl)tetramethylenediamine,N,N'-bis-(4-methylaminophenyl)tetramethylenediamine orN,N'-bis(ethyl)-N,N'-bis(4'-amino-3'-methylphenyl)-ethylenediamine. 10.A composition according to claim 1, wherein said at least one oxidationbase isN,N'-bis(β-hydroxy-ethyl)-N,N'-bis(4'-aminophenyl)-1,3-diaminopropanolor an acid addition salt thereof.
 11. A composition according to claim1, wherein said acid addition salt is a hydrochloride, a hydrobromide, asulphate or a tartrate.
 12. A composition according to claim 1, whereinsaid at least one oxidation base is present in a concentration rangingfrom 0.0005 to 12% by weight relative to the total weight of saidcomposition.
 13. A composition according to claim 12, wherein said atleast one oxidation base is present in a concentration ranging from0.005 to 6% by weight relative to the total weight of said composition.14. A composition according to claim 1, wherein said at least one firstcoupler is present in a concentration ranging from 0.0001 to 10% byweight relative to the total weight of said composition.
 15. Acomposition according to claim 14, wherein said at least one firstcoupler is present in a concentration ranging from 0.005 to 5% by weightrelative to the total weight of said composition.
 16. A compositionaccording to claim 1, wherein said at least one second coupler ispresent in a concentration ranging from 0.0001 to 10% by weight relativeto the total weight of said composition.
 17. A composition according toclaim 16, wherein said at least one second coupler is present in aconcentration ranging from 0.005 to 5% by weight relative to the totalweight of said composition.
 18. A composition according to claim 1,wherein said medium suitable for dyeing comprises water or a mixture ofwater and at least one organic solvent.
 19. A composition according toclaim 18, wherein said at least one organic solvent is a C₁ -C₄ loweralkanol, a glycerol, a glycol ether, or an aromatic alcohol.
 20. Acomposition according to claim 1, wherein said composition has a pHranging from 3 to
 12. 21. A composition according to claim 1, whereinsaid composition is in the form of a liquid, a cream, a gel, or any formsuitable for dyeing keratin fibers.
 22. A process for dyeing keratinfibers comprising applying an effective amount of at least onecomposition according to claim 1 to said keratin fibers and developingcolor at acidic, neutral or alkaline pH by adding an oxidizing agent.23. A process according to claim 22, wherein said oxidizing agent eitheris added to said composition at or prior to the time of application tothe keratin fibers, or is present in an oxidizing composition that issimultaneously or sequentially applied in a separate manner.
 24. Aprocess according to claim 22, wherein said keratin fibers are humanhair.
 25. A process according to claim 22, wherein said oxidizing agentis hydrogen peroxide, urea peroxide, an alkali metal bromate or apersalt.
 26. A process according to claim 25, wherein said persalt is aperborate or a persulphate.
 27. A process according to claim 22, whereinsaid oxidizing agent is hydrogen peroxide.
 28. A process according toclaim 22, further comprising leaving said composition on said keratinfibers for a time ranging from 3 to 50 minutes, and then rinsing saidkeratin fibers, washing said keratin fibers with shampoo, rinsing saidkeratin fibers again and drying said keratin fibers.
 29. A processaccording to claim 28, wherein said time ranges from 5 to 30 minutes.30. A multi-compartment device or multi-compartment dyeing kit, whereinsaid device comprises a first compartment containing at least onecomposition for the oxidation dyeing of keratin fibers according toclaim 1, and a second compartment containing an oxidizing composition.31. A composition according to claim 1, wherein said at least oneoxidation base is paraphenylenediamine, said at least one first coupleris 3-aminophenol, and said at least one second coupler is4-hydroxyindoline.